CA2188550A1 - Stable automotive aqueous metallic-flake tint dispersion - Google Patents
Stable automotive aqueous metallic-flake tint dispersionInfo
- Publication number
- CA2188550A1 CA2188550A1 CA002188550A CA2188550A CA2188550A1 CA 2188550 A1 CA2188550 A1 CA 2188550A1 CA 002188550 A CA002188550 A CA 002188550A CA 2188550 A CA2188550 A CA 2188550A CA 2188550 A1 CA2188550 A1 CA 2188550A1
- Authority
- CA
- Canada
- Prior art keywords
- metallic
- dispersion
- flake
- percent
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/006—Metal
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
A stable, air-dry, low-VOC waterborne metallic flake pigment dispersion containing an aqueous carrier, film-forming binder and metallic-flake pigment and having a solids content of about 10-30 % by weight; wherein the metallic surface is passivated with a hydrophobically-modified aliphatic organic phosphate ester which is subsequently combined with an aqueous resin binder to stabilize the metallic flakes against long-term settling, gassing, floating, and re-agglomeration of flake particles. The VOC of the resulting dispersion is about 5 to 3.5lbs/gallon (minus water) and contains metallic flake pigment-to-binder weight ratio of about 10/100 to 50/100. The dispersion can be used neat as a bright metallic waterborne base coating or combined with other colored dispersions and other compatible resinous materials.
Description
WO95/33010 ~ 2 t 88~5~ r~
Ill L~f STABLEi AUTOMOTlVEi AQUEiOUS
MEiTAT T ;fC FI AKEi TINT DISPERSION
BACKGROUND OF THF INVENTION
The present invention relates to a ~`u~ r~ l; for a ~d~ bulllf metallic-flake tint dispersion and a process of making the same. Specifically, it relates to tints which can be used alone, or more commonly in rnmhinPtinn with 0 other .li~ ; -"~ as an air-dry or baking, low-VOC metallic-flake coating. BothimmPrliqtP and long-term stability of metallic-flake tint .l,~ ."~ are obtained.It is well known in the art that various organic phosphate acid ester agents prevent or retard the reaction of water and aluminum flake, which otherwise may lead to the formation of potentially explosive hydrogen gas and the loss of desirable aesthetic effects. U.S. Pat. No. 4,350,535 disclose metallic-~lake paste ~ ln~ which use such agents. U.S. Pat. No. 4,565,716 and U.S.
Pat. No. 4,717,424 also describe such paste and coating fnrmllhltinnc In all these cases, however, the drawback is that the stability of the metal-containing paint is rlPpf nrlf nt upon how the metal paste or dispersion is mixed with the other paint 2 o ~UlU~UO~ . While it is generally possible to obtain good ~ stability and v.~"uedu dul.,e by ~ul~iciv~l~ly stirring each ~ u ~ in individually, such d~lU~ dll~C cannot be readily achieved when simply combining u ~ in a can (without gradual or ill~ mixing or stirring in of the second ~""'l" "" 1) and then ~ f applying lv;v~vlldLiull (- P~ 1 shaking of 25 the can~ for a short time. The latter ~ vliù.. process is typical of automatic mixing-machine operations employed by: L.~ paint refinishers, especially in the U.S. The result of such a l~ju._~liull process has been aluminum flake which is unstable and not well ill~ul~u-dt~,d into the liquid carrier. The product may even It~fV,~lUlllvldlc and flocculate, have poor aesthetics, or the metallic3 o dispersion may separate from the rest of the paint ~ f t~, which is ~isually perceived as an llrlflf cirPhlP floating pl~f n~ or f`hS'rPrtf'riCtif~` Such defects may occur anytime, from; ... .1 ~ after vj .. until ~r~lir~ltin~ and ,~ drying on a substrate. The maglutude of such a problem will vary depending on such factors as the presence of s~lrfqrt~nfc, solvent parfitioning between the 35 aqueous and particle phases, the shape and flictrihutinn of the metallic particles, surface tension, CVd,UUIdliUII rate of solvents, and the f~ c of the paint.
The present invention allows the user to formulate a metallic ~t~,lbulllc tint dispersion which cvn be used as a paint itself or can be combined WOg5/33010 r~"u.~ -` - 2 1 88550 with other (met~lic or non-metallic) pigmented or non-pigmented wat..l,~ .c . to produce aqueous paints by lcj.l~ dliOIl or by mixing each individually. The result is a paint which when sprayed on a substrate gives stdble and reproducible A;ly~ ul~ ;al brightness, metallic two-tone, adequate hurnidity and water resistance, and dilutability with water as needed to adjust tinting strength, viscosity, and non-volatile content.
SUI~I~ARY OF TT~P INVFNTION
A stable ~.t~.bulllc, low VOC metallic-flake tint dispersion omrricinl; by weight of total dispersion, as follows:
(a) 2 to lS percent of a metallic flake;
(b) 5 to 30 percent of polymeric binder;
(c) 0.l to 3.0 percent by active weight of an organically-modified rhn~rhr~n~A-acid ester; and (d) 55 to 90 percent of an aqueous carrier ~ 2; at least 50 percent water;
wherein the ~ s ~ is made by adding an aqueous resin dispersion ~r~ " by weight of aqueous resin dispersion, 70 to 95 percent water and 5 to 30 percent polymeric material to a sul~..Ll,u...c dispersion of the 2o metal flake containing said 'b ~ modified r~ -acid ester.
The pH of the dispersion can be preferably adjusted (increased) to 7.0-9.0 usmg ammonia or amine. Up to about 1% by weight of tbickener dispersion resin solids can be added to adjust viscosity and increase shear-thimling~ necessaryfor~ to ~t~mr~hil~osandtrucks. The 25 ~ cam be used itself (neat) as a bright metal wal~lbulllC coating or combined (by stirring or l~ liUIl) with aqueous binders and/or colored pigment 1;~ and/or other , ~ resins to form an ~U~UUIUIiVC-quality metallic colorcoat. In any case, the resulting colorcoat or basecoat canthen bc applied over a primed steel or plastic substrate to give colored metallic 3 o basecoats having excellent and stable properties such as adhesion, humidity resistance, brightness and two-tone color (flop) required for eA~terior _u~ul~u~ive ~li~liu~s. This basecoat can be used under a variety of aqueous and non-aqueous clearcoats to provide the same stable properties and also good durability and gldlllUUlUUS ~p~lau~
DpTAn Fn DES~RlErrlON OF T~TP INVENAflON
The ~at.,ll,UluC metallic-flake tint dispersion or r--~ of the present invention may be produced in a two or three step process. In the first , woss/330l0 2 1 8855~
step, the metallic flake (typically a ;U~ ly available paste) is dispersed in asuitable c~ mr~tih~ organic solvent, which also contains a p~a;v~ lg agent, to produce a aul~ bul "c metallic-flake tlicrF rci~n The level of ~ iVd~ agent in this 5O~ JU11IC dispersion is suitably about 1 to 30 percent, preferably 5 to 20 5 percent by weight on metallic flake and the total solids of the dispersion is about 5 to 45 percent by weight. The amount of passivator is suitably adjusted to provide hydrogen gas inhibition by a sufficient amount passivator, but to avoid water s~,~ilivi~y problems with the coating caused by an excess amount of the passivator. Besides aluminum and its alloys, other metals which can be used in o the present invention are zinc, bron~e, brass, copper, iron, ~ c~ and alloys thereof, and mixtures of the foregoing. In particular, there are a multitude of ;UIIllll~ ,ial grade aluminum pigments which are usable in this invention.
Typically, these metallic pigments are non-leafing flakes which are prepared as pastes by a milling process combining aluminum with a lubricant which is typically oleic acid and a pasting agent such as mineral spirits. During cllhcF qll~nt treatment of the material, solvent can be removed, different solvents or water can be added, and inhibiting agents and/or ~ can be added.
The final aluminum paste cnmrr cititm is typically 55-75% :~lllmimlm, 22 44%
liquids, 1-3% oleic acid, and 0-5% inhibitirlg agents and/or ~ These 2 o aluminum pastes carl be either water dispersible or non-~licrF rcihlF~ Such aluminumflakeshaveasize ,l ~l,;l.ul;....whichtypicallyaveragesbetween8and 32 microns, but can be utilized within a range of about 3 to 50 microns. The shape and size ~ - of flakes ~ s to di~ "c~s~ among cu~ ,ially available aluminum pastes, in termc of brilliance, sparkle, two-tone,25 ~ ., and lightness. These ~ ,llc~s may be Yery important and are often exploited in the color design of metallic colorcoats for ~ ~ .. l ~ lF 6 and trucks. Dc;,~i~liu~ of .u"._.,liu~l metallic pigments amd pastes are proYided in the standard reference PIGMENT HANDBOOK, ed. Temple C Patton (Wiley-l - Publication 1973) pages 785-835.
3 û Regarding the first step of the present inYention, mF nti~nF~d aboYe, the ~ ;l /1F liquid organic solYent is one w_ich has partial or complete miscibility with water and includes (but is not limited to) acetone, methyl ethyl ketone, diacetone alcohol, methanol, ethanol, i ~UI~l U~JdllOI, 1-propanol, jcl~blltsln(71 n-butanol, 2-butanol, n-pentanol, 2-pentanol, 2-methyl-1-butanol,methyl amyl alcohol, 2-methyl-1-pentanol, 2-ethyl hexanol, ethyl acetate, propylacetate, butyl acetate, isobutyl acetate, PM acetate, butyl cellosolve acetate, ethyl carbitol, butyl cellosolve, methyl propasol, propyl p}opasol, butyl propasol, t-butyl propasol, water, and any c~mhinqtitmc of such liquids. Preferred organic solvents WO 9sl33olo ' ~
` 4 2188~5a âre those having ev~lJu~Liull rates between 0.2 and 2.0 times the rate of butyl acetate and which have at least 2% miscibility in v,~ater. Preferred examples ofthese are n-butanol, propasol, isu~lul~culûl, ic~ b~-t~nol, and butyl cellosolve.
C~ of n-butanol and n-pentanol are particularly preferred. .
The pa l~;v~Lillg agent is at least one orgarlic ~ ester having a general formula as follows:
R1 - o R--10A)m--~P=O
R2 - o wherein R represents an alkyl group having 12 to 24 carbon atoms or a lû cllhctitllt~d aryl group~ containing at least one alkyl ~l lb~ having l2 to 24 carbon atoms. The group A represents an alkylene group having 2 to 4 carbon atoms, m represents an integer from 1 to 20, and R1 and R2 ;~ ly represent hydrogen, an alkyl group having 12 to 24 carbon atoms, or R-(OA)m (wherein R, A, and m are the same as set forth above). U.S. Patent No. 4,350,535generically describes esters which include the phosphate esters described above for use in this invention. These phosphate esters are c~ n~n~lly available from a variety of sources, including Mona Chemicals (Patterson, NJ.) and Rhone Poulenc (Princeton, NJ.) As stated already, the first step of the invention requires the 2û combining of the metallic flake, organic solvent, and a ~Ja~i~aLiu~ agent. Usually, the metallic flake is added to the mixture of solvent and ~a~ aLi~ agent and mixing is performed by an air-driven mixing blade of ll~cpe~fi~d design.
S~ c heating of the mixture to from 90-160 F is helpful to insure miscibility and uniformity.
Required mixing time will Yary, but a minimum of 90 minutes is typically needed to disperse aluminum flakes adG~Iua~lJ. Additional mixing of several hours can be performed without ~l t ~ - of the aluminum-based aesthetics. High-shear mixing such as a Cowles~ blade mixer should be avoided to prevent bending and splitting of the flakes. Prior to conti~uing to the second 3 o step of the invention, it is preferable to allow the metallic-flake dispersion to remain unmi~ed at room ~ "~ ; for 8-12 hours or more for equilibration and stâbility of the coating. Longer waiting times are p~ lr, but the dispersion will typicaUy begin to show settling of the met llic flake. In any case, the dispersion should be remixed just prior to using in step two.
-WO 95133010 2 ~ 8 ~ 5 5 0 r~
.
In the second step, the met~llic flake dispersion is combined with aqueous binder resin or resins and water to form a tint. Suitable resins includebut are not limited to polymers and ~;uuol~ . of acrylic, a~lyluulc LL~c, p~ s~. ul~ LIl~c, p~lJ~ LL~. ul~.L~ , p~ P ulcl~ullillc formaldehyde, and epoxy ~ s The material is combined by adding each ingredient into a tank -with mixing and stirring for a period not less tban 30 minutes. Typically some rheology control agents, anti-settLng agents, ~ fOaln control agents, ~ tPrincirlloc or other additives are also added, usually after the 30 minutes mix is complete. These are generally used at about ~50% based on flake solids. Also, additional water is typically added, as required, to aid mixing.
The use of associatiYe thickeners as part of the rheology package is preferred for achieving i,l~vl~vl.lLion of the aqueous metallic flake with otherC~ WAL~ll)UIIIC ~ There are at least two types of rhPnlng~
additives. The first is known as alkali-swellable (ASE) latex and the second is associative thickener latex (AT). In one ~ l~n-l; ~ l, a ~I ~I I I1 ); I IA I ;I II I of one ASE
and two AT's is used. Two effective associative thickeners are Rohm ~ Haas's (pl ;l ~lr ~ PA) Acrysolr~ TT-615 and Henkel's (Ambler, PA) DSX-1550r~
th;~-lrPnPrc Each is typically added at a level of about 1-15% by weight based on flake solids, preferably 1-10% of associative thickener latex and 5-15% of alkali-2 o swellable thickener. In one l ~o~ I one ASE and two AT thickeners are used, ~ Acrysol~ ASE-60, Acrysol~ TT-615, and DSX-1550. In this , .l .o l; , l, the three thickeners are added in a specified order during the tint mAAm-fAAA~lre, pH is increased, and then the viscosity is adjusted down to a constant Brookfield viscosity range using deionized water only.
2 5 Ammonia or amine is suitably added to adjust the pH to a level where the thickener resins are activated, typically in the range of 7 to 9. The VOC of the resulting tint dispersion is about Q30 to Q42 kg/l (minus water) which is equivalent to 2.5 to 3.5 Ibs/ gallon (rninus water). The aqueous binderresin ~ added to the sol~ l,ulll~ metallic-flake dispersion suitably 3 o comprises, by weight of the aqueous binder resin, 5 to 30 percent, preferably 10 to 25 percent of polymeric material and 70 to 95 percent, preferably 75 to 90 percent (by weight) water. A preferred example of an aqueous binder resin comprises an acrylic polymer latex and an acrylic polymer hydrosol. See commonly assigned U.S. Patents Nos. 5,166,254; 5,'~19,916; 5,æl,584 and 5,266,406, all hereby hl~ull~ul~t~d by reference. k~ul~u~ ol, or iso~,u,u~vl in ' with jcnhlltA~nnl is preferably used in the hydrosol resin cook for aluminum tint stability. The strength of the ~ ,17UUIIlC metallic-flake dispersion is ~ - ; d by the pigment-to-binder weight ratio which is typically 10/100 to WO 95/33010 r~
~1 8~5~
50/100, but usually 20/100 to 30/100 which will allow nearly all ~ ...u~ivc metallic colors to be matched.
The resulting stable ~ .bu...c, low VOC metallic-flake dispersion (also referred to as a tint) comprises, by weight of the dispersion, 1 to 15 percent, preferably 2 to 10 percent, of a metallic flake; 5 to 30 percent, preferably 10 to 20 percent, of polymeric binder (i.e., binder resin); 0.1 to 3.0 percent, preferably 0.2 to 1.0 percent of an organically-modified 1~ acid ester; and between 55 to 9S percent, preferably 60 to 80 percent of an aqueous solvent ~ between S0 and 90 percent, preferably 60 to 75 percent water.
This ~t~,lbu~ metallic-flake tint or dispersion can be applied as a basecoat itself or combined in any amount with other ~ Ir binders and pigment (metaUic and/or non-metallic) ~ to form an ulllu~ive-quality color coat. For making ~ OIIIU~iVC refinish basecoats, for example, the tints according to the invention are usually combined with various non-metallic colored tints, pearl tints, and/or resin binders (balanced clears.)For example, a final paint may typically comprise a metaUic tint according to the present invenition, a balancing clear (which may be similar to the aqueous resindispersion described above), and three colored tints or ~ " ~ , for example, one black, one white and one red. A tint may be used alone as a paint, for 2 o example, m the case of a silver metallic paint.
When combining with other .~-.-- I,.~ t~ it can be stirred together or more typically added into a container without any stirring and then rejuvenated by hand shaking or by using any of various paint shakers such as RedDevil~, Gyro3~, or Cyclone3D shakers for about 1-S minutes to achieve excellent ill~,Vl,UUld~iUII of aluminum into ~ binders and pigmented dispersion.
L~u~uu~Lu.. is evaluated by observ-ing and measuring physical or chemical changes to the paint over a period of time. TypicaUy, the period of time of interest for any changes wiU be from 1 day to 3 months. Evaluations are typically made on wet paint in the can or after applying films to a substrate. These 3 û changes include viscosity movement, pH drift, color change, metaUic-flake floating, clumping, mottling or settling, and gas pressure build-up in a closed can.
The gas build-up can be l~t~ d by ~ f ~ ... . 1 1ll, ~"l ~,..I.,,l~
weU known in the industry, but in practice is more typically evaluated by checking for oozing-out of a partially vented can or listening for a loud pop or 3 5 hiss soumd which occurs when opening a sealed can. After paint ~rrlir~til onsome substrates, such as dried primer-surfacer or clearcoat, evaluation of f~ lf' l,~ .,L,.~ such as head-on brightness, two-tone (flop), metaUic non-uniformity (mottling) and ~....-ull,,,~ . provide clues to the level of . = = _ = _ ~
WO 95/33010 2 1 8 8 5 5 (~
ill~u~ uu~ iû~ of the w~.t~. bul l.c metallic-flake dispersion. Finally, film properties such as a&esion to substrate and clearcoats, humidity cabinet resistance, and gloss changes in the colorcoat provide other in~lir~ltinnc of the quality of the dispersion and metallic paint. This system as described provides 5 very good ill~,Ul UUl d~iUII of metaDic flake, without sacrificing humidity resiStance, and has good longterm stability.
Application p. .1~.. ,n~ ~ ~ can be variable and is dependent on r~any factors, such as ~l r~ e l ;~ booth rnn-litinn~ number of coats required for hiding, and spray tP~ ~ ~ Two paint l.~ . ,..,.. t~ . ~ which a sprayer wants to have some control over are the viscosity and the non-volatile content of the paint. These t vo p~ . t- , can influence the ;~ ; of the paint out of the spray gun used to apply the paint. Thus, improved dl'J"' '~ is often obtainable through addition of water to the paint This technique is limited, however, due to greater sag tendency and poorer hiding and transfer efficiency of the paint film. The ~ .bUIIIC metallic-flake tint dispersion described is readily dilutable with water as needed to decrease tinting strength, as well as lower viscosity and non-volatile content, without changing VOC level. No loss of metallic aesthetics is seen with water dilution and i~CulyulaLiull is well ", ,,; " I ~
2 o The foDowing examples illustrate the invention. All parts and pc. ~llL~ ,~D are on a weight basis unless otherwise indicated. All molecular weights disclosed herein are ~Pt~rmin~d by gel ~ y using a pG~ llC standard.
F~IP! F 1 This example iDustrates a ~t- ~b~ aluminum dispersion made according to the present invention. In ~ '1l examples, to evaluate its physical paint properties, this ~v~L~,Ibulllc aluminum dispersion is used to make metallic basecoat ~ and evaluated for in-can and sprayed 3 o l ~, r~ compared to SUI~I1IJUIIIC aluminum and its basecoat ~"'l"'`'~;"" Thefinalbasecoat~ areverysimilarin,....~l~o~;l;....
The basecoat, . are prepared by first forming an aluminurn dispersion and then mixing the aluminum dispersion with acrylic latex binder ~ l,. .". .. ~and colored pigment .l;~ The aluminum dispersion itself i5 made in two 3 5 steps, first a Dul~ l,ul -le aluminum dispersion is formed which is then cûmbined with w~t~,lbu~e materials to make a w~l,lbulllc aluminum ~i~rPr~ir,n The following ill~ " were used to make the DUI~ Ll~u--lc aluminum dispersion in step one:
WO 95133010 r~
2 1 ~8550 PART I p~rts by Wt.
n-butanol 439 n-pentanol 1026 5P~IJU~IhYI~1IC stearyl ether phosphate 147 (mixed mono/di ester) aluminum flake paste 1612 (60% solids in min. spirib/lydlu~ulJull solvent) Part 1 was added to an unlined metal gallon can and heated to a te~ l dlUI e of 110 F using a hot water bath. The material was stirred using an5 air-mixer during the heating process. After 10 minutes, the mixture is a CUIII~ .."~. . u..~ liquid. The heating source is then removed, and the batch begins to cool. Then Part 2 is added over several minutes with vigorous stirring. The stirring continues until the aluminum flakes are well dispersed into the solvent/,ullu~,uh~le mixture, about 2 hours. Then the stirring is stopped and 2 o the material is stored for 12 hour3 at rest. The dispersion quality is tested by draw,ng down the dispersion on glass with a controlled film applicator (Q003 doctor blade). This 5~ ..;I)UILIC aluminum dispersion is evaluated versus the wi-lelbulll~ aluminum dispersion made in step 2 below. The W:~lellJUIII~
aluminum dispersion used the following ~6. ~,J;~..b.
p~rtS by Wt.
Acrylic polymer latex 5661.8 Acrylic polymer hydrosol 1769.0 Deionized water 1243.5 Aluminum dispersion from step 1 above 2350.8 35Associative thickener (Henkel DSX-1550) 30.3 Aclysol~ ASE-60 thickener (Rohm & Haas) 173.0 Deionized water 3390.4 Aqueous hydroxide 3% active 410.9 WO 95/33010 ~1 8 ~ 5 5 ~ PCTIUS95/05863 pART 4 Deionized water 1779.2 Acrysol~ associative thickener TT-615 59.0 (Rohm & Haas) 5Defoamer (Balab~ 3056A) 75 Deionized water 1875.2 TOTAL 18750.6 In the above list of i~ L~, the acrylic polymer latex (36% in deionized water) consists of 26.4 parts methyl methacrylate, 50 parts ethylhexylacrylate, 25 parts methylol ~ LI-~ 1P 3 parts ~J.¦IuA~,Ll.~l acrylate, and 3 parts methyl acrylic acid. The acrylic polymer hydrosol (in deionized water, isopropyl alcohol, and isobutyl alcohol) consists of 34 parts methyl Illc;l~ L.L~, 52 parts ethylhexyHI.~,Ll.d~.~L.~, 5 parts methylol Ill."lld~ly' 1~ 3 parts L~I.U~LIIYI acrylate, 3 parts methyl acrylic acid, and 2 parts surfactant. Part 1 .lL~ are added to a 5-gallon lined pail and mixed for 15 minutes Part 2, after re-mixing for 30 minutes, is then added slowly with mixing and allowed to mix rapidly for 60 minutes. Then Part 3 is added one ingredient at a time with 2 o mixing and then allowed to mix for 30 minutes. Finally, Part 4 is added oneingredient at a time with mixing and then allowed to mix for at least 30 minutes.
The viscosity is controlled to 800-1500 cps (Brook~ield 5 RPM at 72 F). The pH
is 83-85 and the P/B (pigment to binder ratio) is 27/100.
2 5 F~xAMpLF~ 2 This example illustrates a charcaol gray metallic basecoat ;. ., . according to the present mvention. The following ill~ ,.lb were combined m a lined quart can:
R~I~P~`ZIt 1 ('r)n~onPnt p~rts by Wt.
Waterborne alurninum dispersion made in 132 Example 1, step 2 Acrylic latex/acrylic copolymer thickened binder 433 35Jet black wdt~,lbulllc dispersion 43 White pearl mica w~t~,.l,wllc dispersion æ
WO 95/33010 " F~
2l 88550 The mixing process was performed in two ways. First, each ingredient was added with mixing by an air mixer. Second, each ingredient was added without mixing and then put on a Red Devil~ j..V~dlOl for 3 minuteS.
COMPARATIVE F.X~ /rPLF. 3 This example illustrates a Cull~ liv~ charcoal gray metallic basecoat (basecoat 2), not according to the present invention, for cr ~ l to the basecoat (basecoat 1) of Example 2 above. The following ingredients were lO combined in another lined quart can:
~.t)nt~rmPnt p~3rtS by Wt.
So~ l,u.llc aluminum dispersion (Example 1, 17 step 1 above) 15Acrylic latex/acrylic copolymer thickened binder 548 Jet black ~dt. lL7ulllc dispersion 43 White pearl mica ~t~ Ibull.c dispersion 22 The mixing process was performed in two ways. First, each ingredient was added with mixing by an air mixer. Second, each ingredient was added without mixing and then put on a Red Devil~ lUI for 3 minutes.
25 FxAMpLF~ 4 This ex~unple illustrates a silver metallic basecoat ~
(basecoat 3) according to the present invention. The following ingredients were combined in a lined quart can:
('.orn~onent p7lrtS by Wt.
Aluminum dispersion (step 2 420 from Example 1) Acrylic latex/acrylic copolymer thickened binder 210 The basecoat ~ ;r "~ above are controlled to a viscosity of 700-1200 cps (Brookfield 5 RE'M, 72 F). The pH is controlled to 8.'-8.6 using WO 95/33010 .~ ~ 8~S 5 ~ r~
aqueous armnonia and/or deionized water as needed, No additional additives were made to these basecoats. A fraction of each basecoat is set aside on the shelf and in a heated stability ove~ to measure the stability with time and . All basecoats were applied to complete hiding over a cured 5 ~.UIIIIIICI~ b~ two~ o~ ~l polyurethane primer-surfacer, which had been applied to clean steel panels. Some ~ O~t~' ;I panels were then clearcoated with a CO~ OI~,lllbulllC two-~ -1 pOI.~ ,lh~C
clearcoat which is allowed to air-dry cure for a IL ~,c .. ~ ' period. Typical film thickness of these coatings are as follows:
Primer- Surfacer û.8-1.2 mils Basecoat 03-0.8 mils Clearcoat 1.0-2.0 mils Data was obtained for both wet and applied paint. In-can (wet) properties are shown in Table 1 below. Film properties are shown in Table 2 below. The results clearly show that basecoat 1 is much better than basecoat 2 15 for floating resistance and also slightly better in humidity 1; r... ".~,.. .
w09s/33010 ~ ' I ` 2 ~ ~ 8~5~ P
1~
o C~ ~o o , ~ ,~ , ~o O O
C~ C~` ~ C~ o x x x x x x --t ~ E ~ ~ ~o ~ ~ ~ x R R
'_ O
R~
t~ R~
O - - C~
O -- _ R~ . ~ R~
C~ C
n ~C . 1 ~ y E ~ ~
~ ~1 R~
.. . . . . . . . . .
WO 95133010 2 ~ 8 8 5 5 PCTNS9sl0s863 V ~ C ,~
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WO 95/33010 2 ~ 8 8 ~ r~~
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j F.XAMPJ ,F, 5 An aluminum ~ b~ ., dispersion according to the present invention is made in two steps as follov s. In step one, the following ingredients are used:
~, ~
Ethylene glycol monobutyl ether 80.0 n-Butanol 30 0 Ethylene glycol monohe~yl ether 20.0 P~ JA~LIlYl~ stearyl ether phosphate 17.0 (mixed mono/di ester) pART 2 Aluminum flaAe paste (60% solids in mineral spirits and aromatic I~IIU~ II) 147.0 TOTAL 294.0 2 0 Part 1 was added to an unlined metal pint can and heated to a t,1 ..... ,.1.,, i of 130F using a hot-water bath. The material is stirred using an air-mixer during the heating process. After 15 minutes, the mixture is a ~ t~
h~.. r,~" ..r~ liquid. The heating source is removed, and the batch cools to 70F.
Then Part 2 is added over 2 minutes with vigorous stirring. Stirring is contmued25 for 1.5 hours. Then the stirring was ~icrr~ntinllpd and the dispersion was left for 36 hours ul-d;~Lulb~d. In step 2, the following ingredients were used:
p~rtS by Wt.
Acrylic polymer latex 127.0 3 o Acrylic polymer latex 207.0 Deionized water 56.0 Aluminum dispersion from above step 127.0 10% Acrysol AS~60~ thickener 94.0 (Rohm & Haas) in deionized water WO 95/33010 ~1 ~ 8 5 ~ ~ r~
Deionized wa~er 152.0 Aqueous ammor'~a (3% active) 12.0 Defoamer (Balab~D 3056A) 10.0 Acrysol ASE-600 (25%) thickener 55 0 in deionized water TOTAL 830.0 The first acrylic polymer latex was the same as used in Example 1 above. The second acrylic polymer latex is made in two stages and comprises 13 percent methyl Ill~Ll~a.,l~ldlc, 2 percent aUyl Ill~,LLacl ~laLe~ and 62 percent butyl acrylate as core m~nnm~.r~, and 3 percent methacrylic acid, 5 percent hexylethyl5 acrylate, and 15 percent butyl acrylate as shell n~r.nnm~rc Part 1 ingredients are added to a lined quart can and mixed for 15 minutes. Part 2, after remixing 15 minutes, is added slowly with mixing and allowed to mix 45 minutes. Part 3 is added one-irlgredient at a time and mixed for 30 minutes. Finally, Part 4 is added and mixed for 15 minutes. The final viscosity is 2540 cps (Brookfield #2, 5 RPM)2 o at a pH of 6.74.
This examples illustrates another charcoal gray metallic baecoat ~ u."l' :' ...,. (basecoat 4) according to the present inventio~ The following 2 5 ~ - ,t~ were used:
C~m~?nn~nt Parts by Weieht WàL~lbulll~, aluminum dispersion 100.0 Step 2 from Example 5 above 3 0 Aluminum-free paint ~ ,. 530.0 Acrylic latex/lu.,la...ll.~ formaldehyde Carbon black waL.,Ibulll~ dispersion Organic blue ~dt~,-bulll~ dispersion Mica pearl waterborne dispersion TOTAL 630.0 WO 95/33010 P~
~ 2 1 8~550 The well mixed aluminum dispersion is put in a lined metal quart can. The aluminum-free paint is added to the dispersion without mixing The quart can was sealed closed and placed on a Gyro'lD paint shaker for 2 minutes.
After removing from the shaker, the paint is tested for properties. The results were as follows:
Initial Floating After Shaker: None Floatmg 24 hrs After Shaker: None Brookfield Visc (#2 sp, 5 RPM) 2020 cps After 24 Hours x 75F 2040 cps After 3 Months x 75F 1240 cps After 1 week x 120F 1050 cps The sprayout showed good aluminum l~ri~ ntPtinn and no spitting or 15 clumping umder a c U~ l pol~ hauc clearcoat. The 96-hour hurnidity adhesion was excellent. No ~ occurred when scribing 100 squares and pulling tape. No significant build-up of gas developed in sealed cans storedfor 3 months at 75F or one wk at 120F.
2 o Those skilled in the art will no doubt be able to compose numerous variatiûns ûf the themes disclosed, such as changing the amounts ûf ill~l "
inci~nifi~Antly from those shown, adding innocuous or ~1111111. .,,. IAI,~ Cl1hCtPn~ C~
or ~..l,~l;l"~ equivalent ~ t~ for those shown. Such variations are considered to be within the inventive concept, as defined in the following claims.
:~ s
Ill L~f STABLEi AUTOMOTlVEi AQUEiOUS
MEiTAT T ;fC FI AKEi TINT DISPERSION
BACKGROUND OF THF INVENTION
The present invention relates to a ~`u~ r~ l; for a ~d~ bulllf metallic-flake tint dispersion and a process of making the same. Specifically, it relates to tints which can be used alone, or more commonly in rnmhinPtinn with 0 other .li~ ; -"~ as an air-dry or baking, low-VOC metallic-flake coating. BothimmPrliqtP and long-term stability of metallic-flake tint .l,~ ."~ are obtained.It is well known in the art that various organic phosphate acid ester agents prevent or retard the reaction of water and aluminum flake, which otherwise may lead to the formation of potentially explosive hydrogen gas and the loss of desirable aesthetic effects. U.S. Pat. No. 4,350,535 disclose metallic-~lake paste ~ ln~ which use such agents. U.S. Pat. No. 4,565,716 and U.S.
Pat. No. 4,717,424 also describe such paste and coating fnrmllhltinnc In all these cases, however, the drawback is that the stability of the metal-containing paint is rlPpf nrlf nt upon how the metal paste or dispersion is mixed with the other paint 2 o ~UlU~UO~ . While it is generally possible to obtain good ~ stability and v.~"uedu dul.,e by ~ul~iciv~l~ly stirring each ~ u ~ in individually, such d~lU~ dll~C cannot be readily achieved when simply combining u ~ in a can (without gradual or ill~ mixing or stirring in of the second ~""'l" "" 1) and then ~ f applying lv;v~vlldLiull (- P~ 1 shaking of 25 the can~ for a short time. The latter ~ vliù.. process is typical of automatic mixing-machine operations employed by: L.~ paint refinishers, especially in the U.S. The result of such a l~ju._~liull process has been aluminum flake which is unstable and not well ill~ul~u-dt~,d into the liquid carrier. The product may even It~fV,~lUlllvldlc and flocculate, have poor aesthetics, or the metallic3 o dispersion may separate from the rest of the paint ~ f t~, which is ~isually perceived as an llrlflf cirPhlP floating pl~f n~ or f`hS'rPrtf'riCtif~` Such defects may occur anytime, from; ... .1 ~ after vj .. until ~r~lir~ltin~ and ,~ drying on a substrate. The maglutude of such a problem will vary depending on such factors as the presence of s~lrfqrt~nfc, solvent parfitioning between the 35 aqueous and particle phases, the shape and flictrihutinn of the metallic particles, surface tension, CVd,UUIdliUII rate of solvents, and the f~ c of the paint.
The present invention allows the user to formulate a metallic ~t~,lbulllc tint dispersion which cvn be used as a paint itself or can be combined WOg5/33010 r~"u.~ -` - 2 1 88550 with other (met~lic or non-metallic) pigmented or non-pigmented wat..l,~ .c . to produce aqueous paints by lcj.l~ dliOIl or by mixing each individually. The result is a paint which when sprayed on a substrate gives stdble and reproducible A;ly~ ul~ ;al brightness, metallic two-tone, adequate hurnidity and water resistance, and dilutability with water as needed to adjust tinting strength, viscosity, and non-volatile content.
SUI~I~ARY OF TT~P INVFNTION
A stable ~.t~.bulllc, low VOC metallic-flake tint dispersion omrricinl; by weight of total dispersion, as follows:
(a) 2 to lS percent of a metallic flake;
(b) 5 to 30 percent of polymeric binder;
(c) 0.l to 3.0 percent by active weight of an organically-modified rhn~rhr~n~A-acid ester; and (d) 55 to 90 percent of an aqueous carrier ~ 2; at least 50 percent water;
wherein the ~ s ~ is made by adding an aqueous resin dispersion ~r~ " by weight of aqueous resin dispersion, 70 to 95 percent water and 5 to 30 percent polymeric material to a sul~..Ll,u...c dispersion of the 2o metal flake containing said 'b ~ modified r~ -acid ester.
The pH of the dispersion can be preferably adjusted (increased) to 7.0-9.0 usmg ammonia or amine. Up to about 1% by weight of tbickener dispersion resin solids can be added to adjust viscosity and increase shear-thimling~ necessaryfor~ to ~t~mr~hil~osandtrucks. The 25 ~ cam be used itself (neat) as a bright metal wal~lbulllC coating or combined (by stirring or l~ liUIl) with aqueous binders and/or colored pigment 1;~ and/or other , ~ resins to form an ~U~UUIUIiVC-quality metallic colorcoat. In any case, the resulting colorcoat or basecoat canthen bc applied over a primed steel or plastic substrate to give colored metallic 3 o basecoats having excellent and stable properties such as adhesion, humidity resistance, brightness and two-tone color (flop) required for eA~terior _u~ul~u~ive ~li~liu~s. This basecoat can be used under a variety of aqueous and non-aqueous clearcoats to provide the same stable properties and also good durability and gldlllUUlUUS ~p~lau~
DpTAn Fn DES~RlErrlON OF T~TP INVENAflON
The ~at.,ll,UluC metallic-flake tint dispersion or r--~ of the present invention may be produced in a two or three step process. In the first , woss/330l0 2 1 8855~
step, the metallic flake (typically a ;U~ ly available paste) is dispersed in asuitable c~ mr~tih~ organic solvent, which also contains a p~a;v~ lg agent, to produce a aul~ bul "c metallic-flake tlicrF rci~n The level of ~ iVd~ agent in this 5O~ JU11IC dispersion is suitably about 1 to 30 percent, preferably 5 to 20 5 percent by weight on metallic flake and the total solids of the dispersion is about 5 to 45 percent by weight. The amount of passivator is suitably adjusted to provide hydrogen gas inhibition by a sufficient amount passivator, but to avoid water s~,~ilivi~y problems with the coating caused by an excess amount of the passivator. Besides aluminum and its alloys, other metals which can be used in o the present invention are zinc, bron~e, brass, copper, iron, ~ c~ and alloys thereof, and mixtures of the foregoing. In particular, there are a multitude of ;UIIllll~ ,ial grade aluminum pigments which are usable in this invention.
Typically, these metallic pigments are non-leafing flakes which are prepared as pastes by a milling process combining aluminum with a lubricant which is typically oleic acid and a pasting agent such as mineral spirits. During cllhcF qll~nt treatment of the material, solvent can be removed, different solvents or water can be added, and inhibiting agents and/or ~ can be added.
The final aluminum paste cnmrr cititm is typically 55-75% :~lllmimlm, 22 44%
liquids, 1-3% oleic acid, and 0-5% inhibitirlg agents and/or ~ These 2 o aluminum pastes carl be either water dispersible or non-~licrF rcihlF~ Such aluminumflakeshaveasize ,l ~l,;l.ul;....whichtypicallyaveragesbetween8and 32 microns, but can be utilized within a range of about 3 to 50 microns. The shape and size ~ - of flakes ~ s to di~ "c~s~ among cu~ ,ially available aluminum pastes, in termc of brilliance, sparkle, two-tone,25 ~ ., and lightness. These ~ ,llc~s may be Yery important and are often exploited in the color design of metallic colorcoats for ~ ~ .. l ~ lF 6 and trucks. Dc;,~i~liu~ of .u"._.,liu~l metallic pigments amd pastes are proYided in the standard reference PIGMENT HANDBOOK, ed. Temple C Patton (Wiley-l - Publication 1973) pages 785-835.
3 û Regarding the first step of the present inYention, mF nti~nF~d aboYe, the ~ ;l /1F liquid organic solYent is one w_ich has partial or complete miscibility with water and includes (but is not limited to) acetone, methyl ethyl ketone, diacetone alcohol, methanol, ethanol, i ~UI~l U~JdllOI, 1-propanol, jcl~blltsln(71 n-butanol, 2-butanol, n-pentanol, 2-pentanol, 2-methyl-1-butanol,methyl amyl alcohol, 2-methyl-1-pentanol, 2-ethyl hexanol, ethyl acetate, propylacetate, butyl acetate, isobutyl acetate, PM acetate, butyl cellosolve acetate, ethyl carbitol, butyl cellosolve, methyl propasol, propyl p}opasol, butyl propasol, t-butyl propasol, water, and any c~mhinqtitmc of such liquids. Preferred organic solvents WO 9sl33olo ' ~
` 4 2188~5a âre those having ev~lJu~Liull rates between 0.2 and 2.0 times the rate of butyl acetate and which have at least 2% miscibility in v,~ater. Preferred examples ofthese are n-butanol, propasol, isu~lul~culûl, ic~ b~-t~nol, and butyl cellosolve.
C~ of n-butanol and n-pentanol are particularly preferred. .
The pa l~;v~Lillg agent is at least one orgarlic ~ ester having a general formula as follows:
R1 - o R--10A)m--~P=O
R2 - o wherein R represents an alkyl group having 12 to 24 carbon atoms or a lû cllhctitllt~d aryl group~ containing at least one alkyl ~l lb~ having l2 to 24 carbon atoms. The group A represents an alkylene group having 2 to 4 carbon atoms, m represents an integer from 1 to 20, and R1 and R2 ;~ ly represent hydrogen, an alkyl group having 12 to 24 carbon atoms, or R-(OA)m (wherein R, A, and m are the same as set forth above). U.S. Patent No. 4,350,535generically describes esters which include the phosphate esters described above for use in this invention. These phosphate esters are c~ n~n~lly available from a variety of sources, including Mona Chemicals (Patterson, NJ.) and Rhone Poulenc (Princeton, NJ.) As stated already, the first step of the invention requires the 2û combining of the metallic flake, organic solvent, and a ~Ja~i~aLiu~ agent. Usually, the metallic flake is added to the mixture of solvent and ~a~ aLi~ agent and mixing is performed by an air-driven mixing blade of ll~cpe~fi~d design.
S~ c heating of the mixture to from 90-160 F is helpful to insure miscibility and uniformity.
Required mixing time will Yary, but a minimum of 90 minutes is typically needed to disperse aluminum flakes adG~Iua~lJ. Additional mixing of several hours can be performed without ~l t ~ - of the aluminum-based aesthetics. High-shear mixing such as a Cowles~ blade mixer should be avoided to prevent bending and splitting of the flakes. Prior to conti~uing to the second 3 o step of the invention, it is preferable to allow the metallic-flake dispersion to remain unmi~ed at room ~ "~ ; for 8-12 hours or more for equilibration and stâbility of the coating. Longer waiting times are p~ lr, but the dispersion will typicaUy begin to show settling of the met llic flake. In any case, the dispersion should be remixed just prior to using in step two.
-WO 95133010 2 ~ 8 ~ 5 5 0 r~
.
In the second step, the met~llic flake dispersion is combined with aqueous binder resin or resins and water to form a tint. Suitable resins includebut are not limited to polymers and ~;uuol~ . of acrylic, a~lyluulc LL~c, p~ s~. ul~ LIl~c, p~lJ~ LL~. ul~.L~ , p~ P ulcl~ullillc formaldehyde, and epoxy ~ s The material is combined by adding each ingredient into a tank -with mixing and stirring for a period not less tban 30 minutes. Typically some rheology control agents, anti-settLng agents, ~ fOaln control agents, ~ tPrincirlloc or other additives are also added, usually after the 30 minutes mix is complete. These are generally used at about ~50% based on flake solids. Also, additional water is typically added, as required, to aid mixing.
The use of associatiYe thickeners as part of the rheology package is preferred for achieving i,l~vl~vl.lLion of the aqueous metallic flake with otherC~ WAL~ll)UIIIC ~ There are at least two types of rhPnlng~
additives. The first is known as alkali-swellable (ASE) latex and the second is associative thickener latex (AT). In one ~ l~n-l; ~ l, a ~I ~I I I1 ); I IA I ;I II I of one ASE
and two AT's is used. Two effective associative thickeners are Rohm ~ Haas's (pl ;l ~lr ~ PA) Acrysolr~ TT-615 and Henkel's (Ambler, PA) DSX-1550r~
th;~-lrPnPrc Each is typically added at a level of about 1-15% by weight based on flake solids, preferably 1-10% of associative thickener latex and 5-15% of alkali-2 o swellable thickener. In one l ~o~ I one ASE and two AT thickeners are used, ~ Acrysol~ ASE-60, Acrysol~ TT-615, and DSX-1550. In this , .l .o l; , l, the three thickeners are added in a specified order during the tint mAAm-fAAA~lre, pH is increased, and then the viscosity is adjusted down to a constant Brookfield viscosity range using deionized water only.
2 5 Ammonia or amine is suitably added to adjust the pH to a level where the thickener resins are activated, typically in the range of 7 to 9. The VOC of the resulting tint dispersion is about Q30 to Q42 kg/l (minus water) which is equivalent to 2.5 to 3.5 Ibs/ gallon (rninus water). The aqueous binderresin ~ added to the sol~ l,ulll~ metallic-flake dispersion suitably 3 o comprises, by weight of the aqueous binder resin, 5 to 30 percent, preferably 10 to 25 percent of polymeric material and 70 to 95 percent, preferably 75 to 90 percent (by weight) water. A preferred example of an aqueous binder resin comprises an acrylic polymer latex and an acrylic polymer hydrosol. See commonly assigned U.S. Patents Nos. 5,166,254; 5,'~19,916; 5,æl,584 and 5,266,406, all hereby hl~ull~ul~t~d by reference. k~ul~u~ ol, or iso~,u,u~vl in ' with jcnhlltA~nnl is preferably used in the hydrosol resin cook for aluminum tint stability. The strength of the ~ ,17UUIIlC metallic-flake dispersion is ~ - ; d by the pigment-to-binder weight ratio which is typically 10/100 to WO 95/33010 r~
~1 8~5~
50/100, but usually 20/100 to 30/100 which will allow nearly all ~ ...u~ivc metallic colors to be matched.
The resulting stable ~ .bu...c, low VOC metallic-flake dispersion (also referred to as a tint) comprises, by weight of the dispersion, 1 to 15 percent, preferably 2 to 10 percent, of a metallic flake; 5 to 30 percent, preferably 10 to 20 percent, of polymeric binder (i.e., binder resin); 0.1 to 3.0 percent, preferably 0.2 to 1.0 percent of an organically-modified 1~ acid ester; and between 55 to 9S percent, preferably 60 to 80 percent of an aqueous solvent ~ between S0 and 90 percent, preferably 60 to 75 percent water.
This ~t~,lbu~ metallic-flake tint or dispersion can be applied as a basecoat itself or combined in any amount with other ~ Ir binders and pigment (metaUic and/or non-metallic) ~ to form an ulllu~ive-quality color coat. For making ~ OIIIU~iVC refinish basecoats, for example, the tints according to the invention are usually combined with various non-metallic colored tints, pearl tints, and/or resin binders (balanced clears.)For example, a final paint may typically comprise a metaUic tint according to the present invenition, a balancing clear (which may be similar to the aqueous resindispersion described above), and three colored tints or ~ " ~ , for example, one black, one white and one red. A tint may be used alone as a paint, for 2 o example, m the case of a silver metallic paint.
When combining with other .~-.-- I,.~ t~ it can be stirred together or more typically added into a container without any stirring and then rejuvenated by hand shaking or by using any of various paint shakers such as RedDevil~, Gyro3~, or Cyclone3D shakers for about 1-S minutes to achieve excellent ill~,Vl,UUld~iUII of aluminum into ~ binders and pigmented dispersion.
L~u~uu~Lu.. is evaluated by observ-ing and measuring physical or chemical changes to the paint over a period of time. TypicaUy, the period of time of interest for any changes wiU be from 1 day to 3 months. Evaluations are typically made on wet paint in the can or after applying films to a substrate. These 3 û changes include viscosity movement, pH drift, color change, metaUic-flake floating, clumping, mottling or settling, and gas pressure build-up in a closed can.
The gas build-up can be l~t~ d by ~ f ~ ... . 1 1ll, ~"l ~,..I.,,l~
weU known in the industry, but in practice is more typically evaluated by checking for oozing-out of a partially vented can or listening for a loud pop or 3 5 hiss soumd which occurs when opening a sealed can. After paint ~rrlir~til onsome substrates, such as dried primer-surfacer or clearcoat, evaluation of f~ lf' l,~ .,L,.~ such as head-on brightness, two-tone (flop), metaUic non-uniformity (mottling) and ~....-ull,,,~ . provide clues to the level of . = = _ = _ ~
WO 95/33010 2 1 8 8 5 5 (~
ill~u~ uu~ iû~ of the w~.t~. bul l.c metallic-flake dispersion. Finally, film properties such as a&esion to substrate and clearcoats, humidity cabinet resistance, and gloss changes in the colorcoat provide other in~lir~ltinnc of the quality of the dispersion and metallic paint. This system as described provides 5 very good ill~,Ul UUl d~iUII of metaDic flake, without sacrificing humidity resiStance, and has good longterm stability.
Application p. .1~.. ,n~ ~ ~ can be variable and is dependent on r~any factors, such as ~l r~ e l ;~ booth rnn-litinn~ number of coats required for hiding, and spray tP~ ~ ~ Two paint l.~ . ,..,.. t~ . ~ which a sprayer wants to have some control over are the viscosity and the non-volatile content of the paint. These t vo p~ . t- , can influence the ;~ ; of the paint out of the spray gun used to apply the paint. Thus, improved dl'J"' '~ is often obtainable through addition of water to the paint This technique is limited, however, due to greater sag tendency and poorer hiding and transfer efficiency of the paint film. The ~ .bUIIIC metallic-flake tint dispersion described is readily dilutable with water as needed to decrease tinting strength, as well as lower viscosity and non-volatile content, without changing VOC level. No loss of metallic aesthetics is seen with water dilution and i~CulyulaLiull is well ", ,,; " I ~
2 o The foDowing examples illustrate the invention. All parts and pc. ~llL~ ,~D are on a weight basis unless otherwise indicated. All molecular weights disclosed herein are ~Pt~rmin~d by gel ~ y using a pG~ llC standard.
F~IP! F 1 This example iDustrates a ~t- ~b~ aluminum dispersion made according to the present invention. In ~ '1l examples, to evaluate its physical paint properties, this ~v~L~,Ibulllc aluminum dispersion is used to make metallic basecoat ~ and evaluated for in-can and sprayed 3 o l ~, r~ compared to SUI~I1IJUIIIC aluminum and its basecoat ~"'l"'`'~;"" Thefinalbasecoat~ areverysimilarin,....~l~o~;l;....
The basecoat, . are prepared by first forming an aluminurn dispersion and then mixing the aluminum dispersion with acrylic latex binder ~ l,. .". .. ~and colored pigment .l;~ The aluminum dispersion itself i5 made in two 3 5 steps, first a Dul~ l,ul -le aluminum dispersion is formed which is then cûmbined with w~t~,lbu~e materials to make a w~l,lbulllc aluminum ~i~rPr~ir,n The following ill~ " were used to make the DUI~ Ll~u--lc aluminum dispersion in step one:
WO 95133010 r~
2 1 ~8550 PART I p~rts by Wt.
n-butanol 439 n-pentanol 1026 5P~IJU~IhYI~1IC stearyl ether phosphate 147 (mixed mono/di ester) aluminum flake paste 1612 (60% solids in min. spirib/lydlu~ulJull solvent) Part 1 was added to an unlined metal gallon can and heated to a te~ l dlUI e of 110 F using a hot water bath. The material was stirred using an5 air-mixer during the heating process. After 10 minutes, the mixture is a CUIII~ .."~. . u..~ liquid. The heating source is then removed, and the batch begins to cool. Then Part 2 is added over several minutes with vigorous stirring. The stirring continues until the aluminum flakes are well dispersed into the solvent/,ullu~,uh~le mixture, about 2 hours. Then the stirring is stopped and 2 o the material is stored for 12 hour3 at rest. The dispersion quality is tested by draw,ng down the dispersion on glass with a controlled film applicator (Q003 doctor blade). This 5~ ..;I)UILIC aluminum dispersion is evaluated versus the wi-lelbulll~ aluminum dispersion made in step 2 below. The W:~lellJUIII~
aluminum dispersion used the following ~6. ~,J;~..b.
p~rtS by Wt.
Acrylic polymer latex 5661.8 Acrylic polymer hydrosol 1769.0 Deionized water 1243.5 Aluminum dispersion from step 1 above 2350.8 35Associative thickener (Henkel DSX-1550) 30.3 Aclysol~ ASE-60 thickener (Rohm & Haas) 173.0 Deionized water 3390.4 Aqueous hydroxide 3% active 410.9 WO 95/33010 ~1 8 ~ 5 5 ~ PCTIUS95/05863 pART 4 Deionized water 1779.2 Acrysol~ associative thickener TT-615 59.0 (Rohm & Haas) 5Defoamer (Balab~ 3056A) 75 Deionized water 1875.2 TOTAL 18750.6 In the above list of i~ L~, the acrylic polymer latex (36% in deionized water) consists of 26.4 parts methyl methacrylate, 50 parts ethylhexylacrylate, 25 parts methylol ~ LI-~ 1P 3 parts ~J.¦IuA~,Ll.~l acrylate, and 3 parts methyl acrylic acid. The acrylic polymer hydrosol (in deionized water, isopropyl alcohol, and isobutyl alcohol) consists of 34 parts methyl Illc;l~ L.L~, 52 parts ethylhexyHI.~,Ll.d~.~L.~, 5 parts methylol Ill."lld~ly' 1~ 3 parts L~I.U~LIIYI acrylate, 3 parts methyl acrylic acid, and 2 parts surfactant. Part 1 .lL~ are added to a 5-gallon lined pail and mixed for 15 minutes Part 2, after re-mixing for 30 minutes, is then added slowly with mixing and allowed to mix rapidly for 60 minutes. Then Part 3 is added one ingredient at a time with 2 o mixing and then allowed to mix for 30 minutes. Finally, Part 4 is added oneingredient at a time with mixing and then allowed to mix for at least 30 minutes.
The viscosity is controlled to 800-1500 cps (Brook~ield 5 RPM at 72 F). The pH
is 83-85 and the P/B (pigment to binder ratio) is 27/100.
2 5 F~xAMpLF~ 2 This example illustrates a charcaol gray metallic basecoat ;. ., . according to the present mvention. The following ill~ ,.lb were combined m a lined quart can:
R~I~P~`ZIt 1 ('r)n~onPnt p~rts by Wt.
Waterborne alurninum dispersion made in 132 Example 1, step 2 Acrylic latex/acrylic copolymer thickened binder 433 35Jet black wdt~,lbulllc dispersion 43 White pearl mica w~t~,.l,wllc dispersion æ
WO 95/33010 " F~
2l 88550 The mixing process was performed in two ways. First, each ingredient was added with mixing by an air mixer. Second, each ingredient was added without mixing and then put on a Red Devil~ j..V~dlOl for 3 minuteS.
COMPARATIVE F.X~ /rPLF. 3 This example illustrates a Cull~ liv~ charcoal gray metallic basecoat (basecoat 2), not according to the present invention, for cr ~ l to the basecoat (basecoat 1) of Example 2 above. The following ingredients were lO combined in another lined quart can:
~.t)nt~rmPnt p~3rtS by Wt.
So~ l,u.llc aluminum dispersion (Example 1, 17 step 1 above) 15Acrylic latex/acrylic copolymer thickened binder 548 Jet black ~dt. lL7ulllc dispersion 43 White pearl mica ~t~ Ibull.c dispersion 22 The mixing process was performed in two ways. First, each ingredient was added with mixing by an air mixer. Second, each ingredient was added without mixing and then put on a Red Devil~ lUI for 3 minutes.
25 FxAMpLF~ 4 This ex~unple illustrates a silver metallic basecoat ~
(basecoat 3) according to the present invention. The following ingredients were combined in a lined quart can:
('.orn~onent p7lrtS by Wt.
Aluminum dispersion (step 2 420 from Example 1) Acrylic latex/acrylic copolymer thickened binder 210 The basecoat ~ ;r "~ above are controlled to a viscosity of 700-1200 cps (Brookfield 5 RE'M, 72 F). The pH is controlled to 8.'-8.6 using WO 95/33010 .~ ~ 8~S 5 ~ r~
aqueous armnonia and/or deionized water as needed, No additional additives were made to these basecoats. A fraction of each basecoat is set aside on the shelf and in a heated stability ove~ to measure the stability with time and . All basecoats were applied to complete hiding over a cured 5 ~.UIIIIIICI~ b~ two~ o~ ~l polyurethane primer-surfacer, which had been applied to clean steel panels. Some ~ O~t~' ;I panels were then clearcoated with a CO~ OI~,lllbulllC two-~ -1 pOI.~ ,lh~C
clearcoat which is allowed to air-dry cure for a IL ~,c .. ~ ' period. Typical film thickness of these coatings are as follows:
Primer- Surfacer û.8-1.2 mils Basecoat 03-0.8 mils Clearcoat 1.0-2.0 mils Data was obtained for both wet and applied paint. In-can (wet) properties are shown in Table 1 below. Film properties are shown in Table 2 below. The results clearly show that basecoat 1 is much better than basecoat 2 15 for floating resistance and also slightly better in humidity 1; r... ".~,.. .
w09s/33010 ~ ' I ` 2 ~ ~ 8~5~ P
1~
o C~ ~o o , ~ ,~ , ~o O O
C~ C~` ~ C~ o x x x x x x --t ~ E ~ ~ ~o ~ ~ ~ x R R
'_ O
R~
t~ R~
O - - C~
O -- _ R~ . ~ R~
C~ C
n ~C . 1 ~ y E ~ ~
~ ~1 R~
.. . . . . . . . . .
WO 95133010 2 ~ 8 8 5 5 PCTNS9sl0s863 V ~ C ,~
~ u~ = -- v~ V
C Z ~ ~:
_ o V~
o f~ 8 ~ ~ 'r ~ o ~ ~o E <I
Z ~C ~ I i i i i ~i ~ L
_ L~
_~ ~ oC ~ ~ ,,o r_ _ 8 _ L
X _ ~ ~ _ _ -- L ~ Z ~ ~ g ~r ~ L o o zo a~ æ Z
C, .
WO 95/33010 2 ~ 8 8 ~ r~~
~ O ~
o ~ , .~ ~ 8 1 + + ++ + +
1-- X ~D O `D
x o~
e f_ O ~ , O O~
e O ~ ~ + + + + +
a v . c ~ D ~ ` .D
X ~ CC C C
a~ ` 8 ~ ~t +
8 8 o 2 1 88~5:~
j F.XAMPJ ,F, 5 An aluminum ~ b~ ., dispersion according to the present invention is made in two steps as follov s. In step one, the following ingredients are used:
~, ~
Ethylene glycol monobutyl ether 80.0 n-Butanol 30 0 Ethylene glycol monohe~yl ether 20.0 P~ JA~LIlYl~ stearyl ether phosphate 17.0 (mixed mono/di ester) pART 2 Aluminum flaAe paste (60% solids in mineral spirits and aromatic I~IIU~ II) 147.0 TOTAL 294.0 2 0 Part 1 was added to an unlined metal pint can and heated to a t,1 ..... ,.1.,, i of 130F using a hot-water bath. The material is stirred using an air-mixer during the heating process. After 15 minutes, the mixture is a ~ t~
h~.. r,~" ..r~ liquid. The heating source is removed, and the batch cools to 70F.
Then Part 2 is added over 2 minutes with vigorous stirring. Stirring is contmued25 for 1.5 hours. Then the stirring was ~icrr~ntinllpd and the dispersion was left for 36 hours ul-d;~Lulb~d. In step 2, the following ingredients were used:
p~rtS by Wt.
Acrylic polymer latex 127.0 3 o Acrylic polymer latex 207.0 Deionized water 56.0 Aluminum dispersion from above step 127.0 10% Acrysol AS~60~ thickener 94.0 (Rohm & Haas) in deionized water WO 95/33010 ~1 ~ 8 5 ~ ~ r~
Deionized wa~er 152.0 Aqueous ammor'~a (3% active) 12.0 Defoamer (Balab~D 3056A) 10.0 Acrysol ASE-600 (25%) thickener 55 0 in deionized water TOTAL 830.0 The first acrylic polymer latex was the same as used in Example 1 above. The second acrylic polymer latex is made in two stages and comprises 13 percent methyl Ill~Ll~a.,l~ldlc, 2 percent aUyl Ill~,LLacl ~laLe~ and 62 percent butyl acrylate as core m~nnm~.r~, and 3 percent methacrylic acid, 5 percent hexylethyl5 acrylate, and 15 percent butyl acrylate as shell n~r.nnm~rc Part 1 ingredients are added to a lined quart can and mixed for 15 minutes. Part 2, after remixing 15 minutes, is added slowly with mixing and allowed to mix 45 minutes. Part 3 is added one-irlgredient at a time and mixed for 30 minutes. Finally, Part 4 is added and mixed for 15 minutes. The final viscosity is 2540 cps (Brookfield #2, 5 RPM)2 o at a pH of 6.74.
This examples illustrates another charcoal gray metallic baecoat ~ u."l' :' ...,. (basecoat 4) according to the present inventio~ The following 2 5 ~ - ,t~ were used:
C~m~?nn~nt Parts by Weieht WàL~lbulll~, aluminum dispersion 100.0 Step 2 from Example 5 above 3 0 Aluminum-free paint ~ ,. 530.0 Acrylic latex/lu.,la...ll.~ formaldehyde Carbon black waL.,Ibulll~ dispersion Organic blue ~dt~,-bulll~ dispersion Mica pearl waterborne dispersion TOTAL 630.0 WO 95/33010 P~
~ 2 1 8~550 The well mixed aluminum dispersion is put in a lined metal quart can. The aluminum-free paint is added to the dispersion without mixing The quart can was sealed closed and placed on a Gyro'lD paint shaker for 2 minutes.
After removing from the shaker, the paint is tested for properties. The results were as follows:
Initial Floating After Shaker: None Floatmg 24 hrs After Shaker: None Brookfield Visc (#2 sp, 5 RPM) 2020 cps After 24 Hours x 75F 2040 cps After 3 Months x 75F 1240 cps After 1 week x 120F 1050 cps The sprayout showed good aluminum l~ri~ ntPtinn and no spitting or 15 clumping umder a c U~ l pol~ hauc clearcoat. The 96-hour hurnidity adhesion was excellent. No ~ occurred when scribing 100 squares and pulling tape. No significant build-up of gas developed in sealed cans storedfor 3 months at 75F or one wk at 120F.
2 o Those skilled in the art will no doubt be able to compose numerous variatiûns ûf the themes disclosed, such as changing the amounts ûf ill~l "
inci~nifi~Antly from those shown, adding innocuous or ~1111111. .,,. IAI,~ Cl1hCtPn~ C~
or ~..l,~l;l"~ equivalent ~ t~ for those shown. Such variations are considered to be within the inventive concept, as defined in the following claims.
:~ s
Claims (5)
1. A stable waterborne tint composition for use on automotive substrates comprising by weight of the tint composition, as follows:
(a) 2 to 15 percent of a metallic flake;
(b) 5 to 30 percent of an aqueous-dispersible polymeric binder;
(c) 0.1-3.0% by active weight of an organically-modified phosphoric-acid ester; and (d) 55 to 90 percent of an aqueous solvent comprising at least 50 percent water, the balance comprising C2 to C8 alcohol;
wherein the composition is made by adding a resin dispersion comprising 70 to 95 percent water and 5 to 30 percent polymeric material to a solventborne dispersion of the metal flake containing said organically modified phosphoric-acid ester having the formula:
wherein R represents an alkyl group having 12 to 24 carbon atoms or a substituted aryl group, containing at least one alkyl substituent, having 12 to 24 carbon atoms, and wherein the group A represents an alkylene group having 2 to 4 carbon atoms, m represents an integer from 1 to 20, and R1 and R
independently represent hydrogen, an alkyl group having 12 to 24 carbon atoms, or R-(OA)m wherein R, A, and m are the same as set forth above; and wherein composition stability is evidenced by substantially nonfloating metallic flake.
(a) 2 to 15 percent of a metallic flake;
(b) 5 to 30 percent of an aqueous-dispersible polymeric binder;
(c) 0.1-3.0% by active weight of an organically-modified phosphoric-acid ester; and (d) 55 to 90 percent of an aqueous solvent comprising at least 50 percent water, the balance comprising C2 to C8 alcohol;
wherein the composition is made by adding a resin dispersion comprising 70 to 95 percent water and 5 to 30 percent polymeric material to a solventborne dispersion of the metal flake containing said organically modified phosphoric-acid ester having the formula:
wherein R represents an alkyl group having 12 to 24 carbon atoms or a substituted aryl group, containing at least one alkyl substituent, having 12 to 24 carbon atoms, and wherein the group A represents an alkylene group having 2 to 4 carbon atoms, m represents an integer from 1 to 20, and R1 and R
independently represent hydrogen, an alkyl group having 12 to 24 carbon atoms, or R-(OA)m wherein R, A, and m are the same as set forth above; and wherein composition stability is evidenced by substantially nonfloating metallic flake.
2. The composition of claim 1 wherein the metallic flake is aluminum.
3. The composition of claim 1, wherein the binder comprises an acrylic latex dispersion copolymer.
.4. A method for making a stable waterborne low VOC metallic-flake tint dispersion comprising:
(a) mixing a metallic-flake paste comprising, by weight, 55 to 75 percent metallic flake in organic solvent, which contains a passivating agent, to produce a solventborne metallic-flake dispersion, wherein the level of passivating agent in this solventborne dispersion is about 1-30 percent by weight on metallic flake and the total solids of the solventborne metallic-flake dispersion is about 5-45% by weight, wherein the metallic flakes are dispersed for at least 90 minutesand, prior to continuing to step (b) below, the solventborne metallic-flake dispersion remains unmixed at room temperature for at least 8-12 hours; and (b) mixing said solventborne metallic-flake dispersion produced in step (a) with a resin dispersion comprising, by weight of resin dispersion, 5 to 30 percent polymeric material and 70 to 95 percent water;
the passivating agent having the following formula:
wherein R represents an alkyl group having 12 to 24 carbon atoms or a substituted aryl group, containing at least one alkyl substituent, having 12 to 24 carbon atoms, and wherein the group A represents an alkylene group having 2 to
.4. A method for making a stable waterborne low VOC metallic-flake tint dispersion comprising:
(a) mixing a metallic-flake paste comprising, by weight, 55 to 75 percent metallic flake in organic solvent, which contains a passivating agent, to produce a solventborne metallic-flake dispersion, wherein the level of passivating agent in this solventborne dispersion is about 1-30 percent by weight on metallic flake and the total solids of the solventborne metallic-flake dispersion is about 5-45% by weight, wherein the metallic flakes are dispersed for at least 90 minutesand, prior to continuing to step (b) below, the solventborne metallic-flake dispersion remains unmixed at room temperature for at least 8-12 hours; and (b) mixing said solventborne metallic-flake dispersion produced in step (a) with a resin dispersion comprising, by weight of resin dispersion, 5 to 30 percent polymeric material and 70 to 95 percent water;
the passivating agent having the following formula:
wherein R represents an alkyl group having 12 to 24 carbon atoms or a substituted aryl group, containing at least one alkyl substituent, having 12 to 24 carbon atoms, and wherein the group A represents an alkylene group having 2 to
4 carbon atoms, m represents an integer from 1 to 20, and R1 and R2 independently represent hydrogen, an alkyl group having 12 to 24 carbon atoms, or R-(OA)m wherein R, A, and m are the same as set forth above.
5. The method of claim 4, wherein the waterborne metallic-flake dispersion is mixed with at least one other pigment dispersion to form a colorcoat composition for application to an automotive substrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/250,261 | 1994-05-27 | ||
| US08/250,261 US5466286A (en) | 1994-05-27 | 1994-05-27 | Stable automotive aqueous metallic-flake tint dispersion |
| PCT/US1995/005863 WO1995033010A1 (en) | 1994-05-27 | 1995-05-19 | Stable automotive aqueous metallic-flake tint dispersion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2188550A1 true CA2188550A1 (en) | 1995-12-07 |
Family
ID=22947010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002188550A Abandoned CA2188550A1 (en) | 1994-05-27 | 1995-05-19 | Stable automotive aqueous metallic-flake tint dispersion |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5466286A (en) |
| EP (1) | EP0760839B1 (en) |
| JP (1) | JPH10500727A (en) |
| KR (1) | KR100248528B1 (en) |
| CN (1) | CN1076374C (en) |
| BR (1) | BR9507901A (en) |
| CA (1) | CA2188550A1 (en) |
| DE (1) | DE69504335T2 (en) |
| MX (1) | MX9605849A (en) |
| WO (1) | WO1995033010A1 (en) |
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| AU677657B2 (en) * | 1993-05-26 | 1997-05-01 | Eckart-Werke, Standard Bronzepulver-Werke, Carl Eckart Gmbh & Co. | Metal-pigment dispersions, method of producing them and their use |
| FR2734835B1 (en) * | 1995-09-22 | 1997-07-25 | Zschimmer Schwarz France | METHOD FOR MODIFYING THE SURFACE PROPERTIES OF AQUEOUS SUSPENSION PARTICLES AND APPLICATIONS THEREOF |
| CN1061670C (en) * | 1997-05-21 | 2001-02-07 | 褚炎明 | Namometre automotive metal finish |
| JPH1157605A (en) * | 1997-08-26 | 1999-03-02 | Kansai Paint Co Ltd | Metallic coating method |
| DE19750519A1 (en) * | 1997-11-14 | 1999-05-20 | Worwag Lack Farbenfabrik Gmbh | Liquid effect paint and process for producing a liquid effect paint |
| US6204319B1 (en) | 1998-10-30 | 2001-03-20 | E.I. Du Pont De Nemours And Company | Aqueous coating compositions |
| US6660793B1 (en) | 2000-06-15 | 2003-12-09 | E. I. Du Pont De Nemours And Company | Aqueous coating compositions having improved transparency |
| DE10114446A1 (en) * | 2001-03-23 | 2002-09-26 | Eckart Standard Bronzepulver | Flat iron pigment used paints, plastics, printing, glass, ceramics and cosmetics comprises reduced carbonyl iron powder |
| US6863718B2 (en) | 2001-10-31 | 2005-03-08 | Silberline Manufacturing Co., Inc. | Phosphonic acid derivative treatment of metallic flakes |
| JP4670069B2 (en) * | 2003-05-30 | 2011-04-13 | 本田技研工業株式会社 | Glittering film forming method and painted product |
| US20050031873A1 (en) * | 2003-08-04 | 2005-02-10 | Guenter Berschel | Method for multi-coat refinishing of substrates |
| JP2005132928A (en) * | 2003-10-29 | 2005-05-26 | Nippon Bee Chemical Co Ltd | Water-base coating material |
| JP2005132927A (en) * | 2003-10-29 | 2005-05-26 | Nippon Bee Chemical Co Ltd | Water-base metallic coating material for automotive interior material |
| EP1789486B1 (en) * | 2004-08-26 | 2008-01-09 | Lubrizol Advanced Materials, Inc. | Coating compositions having improved stability |
| CN101760071B (en) * | 2008-12-23 | 2012-06-27 | 上海涂料有限公司技术中心 | Method for using solvent type resin aluminum pigment in water paint |
| CN102167941B (en) * | 2010-02-26 | 2012-12-19 | 温州邦轩科技有限公司 | Aqueous plastic coating paint |
| CN102101956B (en) * | 2010-12-30 | 2012-08-01 | 山东科技大学 | Preparation method of low-carbon light reflecting energy-saving coating |
| CN102020918B (en) * | 2011-01-11 | 2012-07-25 | 深圳市广田环保涂料有限公司 | Polyurethane paint as well as preparation method and use method thereof |
| CN102229782B (en) * | 2011-06-20 | 2013-07-24 | 上虞市佑谦特种材料有限公司 | PU elastic paint |
| CN102277075A (en) * | 2011-07-25 | 2011-12-14 | 东来涂料技术（上海）有限公司 | Aqueous automobile repairing paint capable of low-temperature construction and preparation method thereof |
| CN102277076A (en) * | 2011-07-25 | 2011-12-14 | 东来涂料技术（上海）有限公司 | Low-temperature aqueous double-component metal effect paint and preparation method thereof |
| CN102504667A (en) * | 2011-11-22 | 2012-06-20 | 大连理工大学 | Aqueous environmental-friendly nanometer structure automobile priming paint and preparation method thereof |
| CN102516863A (en) * | 2011-11-22 | 2012-06-27 | 大连理工大学 | Water dispersible environmentally-friendly nanometer structure automotive finish paint and preparation method thereof |
| CN102504694A (en) * | 2011-12-19 | 2012-06-20 | 大连理工大学 | Water-based naon-sized pre-coated coil top coating and preparation method thereof |
| CN102516850A (en) * | 2011-12-19 | 2012-06-27 | 大连理工大学 | Aqueous nano composite electrically-conducting paint and preparation method thereof |
| CN102604445A (en) * | 2012-02-15 | 2012-07-25 | 合肥旭阳铝颜料有限公司 | Preparation method of aluminum pigment with high voltage breakdown resistance |
| CN102604444A (en) * | 2012-02-15 | 2012-07-25 | 合肥旭阳铝颜料有限公司 | Preparation method of water-based aluminum pigment for external wall heat insulation |
| CN102604443A (en) * | 2012-02-15 | 2012-07-25 | 合肥旭阳铝颜料有限公司 | Preparation method of water-based high flash aluminum pigment for automobiles |
| WO2013170007A1 (en) * | 2012-05-11 | 2013-11-14 | U.S. Coatings Ip Co. Llc | Aqueous coating composition having stabilized color pigments |
| CN102796438A (en) * | 2012-08-16 | 2012-11-28 | 广州立邦涂料有限公司 | Orange peel pattern wrinkled epoxy floor paint and its preparation method |
| CN102876167B (en) * | 2012-10-08 | 2015-03-18 | 浙江圣力邦漆业有限公司 | Aqueous silvery aluminum powder flashing paint |
| EP3252118B1 (en) * | 2015-01-28 | 2019-10-30 | Kansai Paint Co., Ltd | Aqueous coating composition |
| CA2974183C (en) | 2015-01-29 | 2020-09-22 | Kansai Paint Co., Ltd. | Method for forming multilayer coating film |
| CA2974184C (en) * | 2015-01-29 | 2019-04-23 | Kansai Paint Co., Ltd. | Aqueous coating composition |
| JP6567566B2 (en) * | 2015-01-30 | 2019-08-28 | 関西ペイント株式会社 | Multi-layer coating formation method |
| US9777180B2 (en) | 2015-02-03 | 2017-10-03 | Basf Coatings Gmbh | Method of forming a passivated pigment slurry for an aqueous topcoat coating composition |
| US10273371B2 (en) | 2016-07-25 | 2019-04-30 | Basf Coatings Gmbh | Method of forming a slurry of encapsulated pigment for an aqueous topcoat coating composition |
| US10781333B2 (en) * | 2017-08-10 | 2020-09-22 | Axalta Coating Systems Ip Co., Llc | Coating adhesion promotors and methods of using the same |
| WO2022076269A1 (en) * | 2020-10-05 | 2022-04-14 | Ppg Industries Ohio, Inc. | High transfer efficiency application methods and shear thinning coating compositions for application using the methods |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS608057B2 (en) * | 1979-05-28 | 1985-02-28 | 旭化成株式会社 | Water-dispersible metal powder composition |
| AT372696B (en) * | 1981-12-18 | 1983-11-10 | Vianova Kunstharz Ag | METHOD FOR STABILIZING METAL PIGMENTS AGAINST CORROSIVE MEDIA |
| US4565716A (en) * | 1983-07-05 | 1986-01-21 | Aluminum Company Of America | Water resistant aluminum particles and coating |
| GB8606915D0 (en) * | 1986-03-20 | 1986-04-23 | Ici Plc | Coating compositions |
| JPH0662886B2 (en) * | 1986-08-20 | 1994-08-17 | 大日精化工業株式会社 | Pigment composition |
| JPH0645764B2 (en) * | 1988-06-24 | 1994-06-15 | 日本ペイント株式会社 | Metal pigment composition |
| JPH06104789B2 (en) * | 1989-03-31 | 1994-12-21 | 日本ペイント株式会社 | Metal pigment composition and aqueous coating composition containing the same |
| CA2014539C (en) * | 1989-04-17 | 2000-07-25 | Shinichiro Umeda | Water borne metallic coating composition |
| DE69125324T2 (en) * | 1990-07-13 | 1998-01-02 | Basf Corp | Metallic, aqueous base coat composition |
-
1994
- 1994-05-27 US US08/250,261 patent/US5466286A/en not_active Expired - Fee Related
-
1995
- 1995-05-19 CA CA002188550A patent/CA2188550A1/en not_active Abandoned
- 1995-05-19 JP JP8500048A patent/JPH10500727A/en active Pending
- 1995-05-19 MX MX9605849A patent/MX9605849A/en not_active IP Right Cessation
- 1995-05-19 WO PCT/US1995/005863 patent/WO1995033010A1/en active IP Right Grant
- 1995-05-19 CN CN95193301A patent/CN1076374C/en not_active Expired - Fee Related
- 1995-05-19 DE DE69504335T patent/DE69504335T2/en not_active Expired - Fee Related
- 1995-05-19 EP EP95919130A patent/EP0760839B1/en not_active Expired - Lifetime
- 1995-05-19 KR KR1019960706693A patent/KR100248528B1/en not_active IP Right Cessation
- 1995-05-19 BR BR9507901A patent/BR9507901A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| BR9507901A (en) | 1997-09-16 |
| EP0760839A1 (en) | 1997-03-12 |
| EP0760839B1 (en) | 1998-08-26 |
| JPH10500727A (en) | 1998-01-20 |
| US5466286A (en) | 1995-11-14 |
| KR100248528B1 (en) | 2000-04-01 |
| MX9605849A (en) | 1997-12-31 |
| CN1076374C (en) | 2001-12-19 |
| CN1149308A (en) | 1997-05-07 |
| KR970703399A (en) | 1997-07-03 |
| WO1995033010A1 (en) | 1995-12-07 |
| DE69504335D1 (en) | 1998-10-01 |
| DE69504335T2 (en) | 1999-02-25 |
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